CN108318510B - The Pt/SnO2 nano particle cluster gas sensor and preparation method thereof of RGO package - Google Patents
The Pt/SnO2 nano particle cluster gas sensor and preparation method thereof of RGO package Download PDFInfo
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Abstract
The present invention relates to a kind of platinum/tin oxide nano particles cluster gas sensors and preparation method thereof of redox graphene package；The composite structure is class core-shell structure, wherein pt atom is evenly distributed on the surface of stannic oxide, forms nano particle cluster as kernel, redox graphene is coated on the surface of entire kernel as shell.The present invention for sensor in the prior art there are sensitivity it is low, operating temperature is high, high production cost, complicated preparation process the problems such as, provide a kind of platinum/tin oxide nano particles cluster gas sensor and preparation method thereof of redox graphene package, methanol sensor prepared by the present invention can realize highly sensitive detection at a temperature of 110 DEG C, it is enable to respond quickly, is provided simultaneously with very high stability；In addition, preparation method of the present invention is simple, controllable, production cost is low, it is easy to accomplish large-scale production, great application prospect.
Description
Technical field
The present invention relates to gas sensor technical fields, specifically, being related to a kind of platinum/bis- of redox graphene package
Tin oxide nanoparticles cluster gas sensor and preparation method thereof.
Background technique
The daily life and production of the mankind is closely related with the environment of surrounding, and the presence of pernicious gas will produce in ambient enviroment
Raw strong influence will bring serious harm even dead if there are poisonous gas for gas.Methanol is a kind of coal through gasifying
The simple chemicals synthesized on a large scale with day hot gas through steam reformation, is important Elementary Chemical Industry product and Organic Chemicals.
In addition, in world's basic organic chemical raw material, methanol consumption figure is only secondary with ethylene, propylene, benzene, occupies the 4th, is that performance is excellent
The good energy and vehicle fuel, methanol is added in gasoline according to a certain percentage can be improved octane number and oxygen content, make to burn
It is more abundant, engine exhaust emission pollutant is effectively reduced.Apply also for fine chemistry industry, the fields such as plastics, for manufacturing
A variety of organic products such as formaldehyde, acetic acid, methylamine, while being also one of pesticide, the important source material of medicine.
Methanol is a kind of substance with more virulent property, colourless alcohol smell, to the nervous system and hematological system of human body
It will cause damage.Contact methanol be more than a certain concentration and time, will occur headache, nausea, have a stomach-ache, be tired, eye-blurred even
Blindness, may finally threat to life.In recent years, there are many safety accident caused by methanol, cause great life, property damage
It loses, therefore methanol concentration in environment is measured in real time, protection staff, production safety are of great significance.
The detection method of methanol gas mainly has chemical measure and instrument detection method.Chemical measure is easy to operate, but
The disadvantages of that there are sensitivity is not high, poor repeatability.Chemical apparatuses detection mainly utilizes its core component: gas sensor carries out
Detection has the advantages such as high sensitivity, reusable, automation, is widely applied in industrial production and environment measuring.Gas
Dependent sensor specifically includes that Semiconductor gas sensors sensing, catalytic combustion type, electrochemistry, infrared ray are examined according to different working principles
Survey, surface acoustic wave etc., wherein there are semiconductor gas sensor the advantages such as high sensitivity, stability be good to be most widely used.
Wherein, the gas sensor occupation rate of market of traditional metal oxide production is maximum, and high stability, cost is relatively low, but same
When operating temperature it is higher (> 200 DEG C), greatly increase the design complexity resistant to high temperatures of its attached detection unit, and there are energy
Higher disadvantage is consumed, while increasing its risk applied in harsh environment, therefore is badly in need of exploitation to work under lower temperature
Methanol gas sensor technology of preparing.
Since two-dimensional graphene in 2004 is found, because of its excellent physics, chemical property, becomes and prepared gas sensing
The preferred material of device.And wherein it is found that Graphene derivative such as redox graphene (RGO) and traditional metal aoxidize
The compound gas-sensitive property that can effectively improve sensor of object, can be effectively reduced operating temperature, has become a hot topic of research direction.
Prior art discloses the preparation methods of a variety of methanol sensors.For example, patent application CN105651835 A is disclosed
A kind of methanol gas sensor preparation method, gas sensitive use graphene oxide doped Sn (bipyO2)2Cl2Material composition,
But the requirement of its synthetic material is excessively high, needs special preparation, and response sensitivity is too low (being 2 under 500ppm).
Patent application CN105699439A discloses a kind of based on carbonitride carried metal and metal oxide composite
Methanol gas sensor preparation method.This method is mainly molybdenum oxide/dioxy of the In-situ reaction cobalt doped on carbonitride
Change titanium nanometer sheet, using the big specific surface area of the material, mesoporous high gas absorption characteristic and electron transmission by material surface gas
Change and influence sensitive many characteristics, realizes the detection to methanol.But that there are persursor material prices is higher for this method, preparation
The problems such as condition is more demanding, it is difficult to realize low cost, the preparation of high-performance methanol gas sensor.
Patent application CN104897727A discloses a kind of gas sensor of highly sensitive more gas detections, mainly to receive
Rice nickel oxide is gas sensitive, powers on chemical deposited nickel atomic layer in ito glass by three-electrode system, then by simple
The processing such as annealing, cooling, ultrasound, obtains the nano-nickel oxide of rose-shaped pattern, makes gas sensor afterwards, and 350 DEG C
Under, response reaches 7 under 5ppm methanol concentration.But it is excessively high that there are still operating temperatures, the not high problem of sensitivity.
Patent application CN104034758A discloses a specific admixture graphene film, noble metal and metal oxide materials
Integrated hydrogen sensor and preparation method thereof, sensor includes substrate, heating electrode, thermally conductive insulating layer, detecting electrode, heating
Electrode is located on substrate, and thermally conductive insulating layer further includes the gold being deposited on detecting electrode between heating electrode and detecting electrode
Belong to sull, the noble metal deposited on metal-oxide film surface, graphene film, which is covered on, is deposited with noble metal
On the metal-oxide film of particle.But there is detection sensitivity difference when low-temperature working in this sensor.
To sum up, methanol sensor in the prior art is low there are sensitivity and operating temperature height, production cost height etc. are asked
Therefore topic develops that a kind of processing step is simple, repeat, high sensitivity and the methanol sensor that can be worked at a lower temperature
Great application prospect and market value；Therefore, it is necessary to develop a kind of new gas sensor.
Summary of the invention
That there are sensitivity is low, operating temperature is high for sensor in the prior art, high production cost, preparation process complexity etc.
Problem, the present invention is intended to provide a kind of platinum/stannic oxide (Pt/SnO of redox graphene package2) nano particle cluster gas
Dependent sensor and preparation method thereof, methanol sensor prepared by the present invention can realize highly sensitive detection, energy at a temperature of 110 DEG C
Enough quick responses, are provided simultaneously with very high stability；In addition, preparation method of the present invention is simple, controllable, production cost is low, it is easy to
Realize large-scale production, great application prospect.
An object of the present invention is to provide a kind of Pt/SnO of redox graphene package2Nano particle cluster.
The second object of the present invention is to provide a kind of Pt/SnO of redox graphene package2The system of nano particle cluster
Preparation Method.
The third object of the present invention is to provide a kind of Pt/SnO of redox graphene package2Nano particle cluster air-sensitive
The preparation method of sensor.
The fourth object of the present invention is to provide the Pt/SnO of above-mentioned redox graphene package2Nano particle cluster and its
The application of preparation method and the sensor of nano particle cluster preparation.
For achieving the above object, the invention discloses following technical proposals:
Firstly, the invention discloses a kind of Pt/SnO of redox graphene package for being used to prepare gas sensor2
Nano particle cluster；The nano particle cluster is class core-shell structure, wherein pt atom is evenly distributed on stannic oxide
Surface forms nano particle cluster as kernel, and redox graphene is coated on the surface of entire kernel as shell.
Secondly, the invention discloses a kind of Pt/SnO of redox graphene package2The preparation side of nano particle cluster
Method；Specifically, the preparation method comprises the following steps:
1) it takes a certain amount of water-soluble stannide to dissolve in solvent, stirs, obtain homogeneous transparent solution, it then will be a certain amount of
Dimethylformamide mixed with above-mentioned clear solution, obtain mixed liquor.
2) in the deionized water that graphene oxide powder is added, also original place is carried out with hydroiodic acid solution after ultrasonic disperse
Reason, obtains redox graphene solution.The reason of selecting hydroiodic acid is: hydroiodic acid guarantee restores partial oxidation of graphite alkene,
Reducing degree is controlled by the time of control reaction, it is subsequent to be dried sample by vacuum drying oven, increase the knot with substrate
It closes, device can be greatly increased to the response characteristic of methanol by redox graphene, and and Pt/SnO2Nano particle cluster is total
Same-action increases the sensitivity of device.
3) it configures precursor solution: taking a certain amount of platinum acid chloride solution to be added in the mixed liquor of step 1), be then added
Solution pH value is adjusted to alkalinity, obtains milky precursor solution by alkaline matter.
4) after mixing the redox graphene solution in step 2) with the precursor solution in step 3), liner is added
To carry out hydrothermal synthesis reaction in the container of polytetrafluoroethylene (PTFE).Hydrothermal synthesis reaction can be by abundant redox graphene, finally
Graphene oxide is completely reduced acquisition redox graphene.
5) hydrothermal synthesis reaction in step 4) is finished and is put into solution and is centrifuged, ethyl alcohol and deionization are used after separation
Water repeats to rinse respectively, is centrifuged, rinses each step, obtains gum-like product.
6) gum-like product in step 5) is dried by two step oven drying methods, is then annealed to get oxygen reduction fossil
The Pt/SnO of black alkene package2Nano particle cluster.
In step 1), the water solubility stannide includes: SnCl4·5H2O、SnCl2·2H2O, SnCl4, dimethyl dichloro
Change tin etc..
In step 1), the volume ratio of the solvent and dimethylformamide is 10:1-30:1.Solvent and dimethylformamide
Additional proportion will affect the grain size of final product.The grain size control for preparing material can be existed in this proportional region
Between 10-50 nanometers, high-specific surface area is obtained, is conducive to promote gas sensitive device performance.
Preferably, the volume ratio of the solvent and dimethylformamide is 20:1.The preferred proportion fully takes into account water-soluble
Property stannide need to meet the operability of later experiments, and the size of this preferred proportion and final product partial size is established and is closed
Connection, to obtain reproducible technique.By controlling the addition volume of dimethylformamide, inhibit the group in material synthesis processes
It is poly-, to achieve the effect that improve material specific area.
In step 1), the solvent is methanol solution；After the addition of methanol and dimethylformamide substance advantageously reduces
The reunion of continuous precursor species, reduces the partial size of material.
In step 1), the mixing time is 30-120min.
In step 2), the concentration of the redox graphene solution is 1-5mg/mL.
In step 3), the alkaline matter includes: NaOH, KOH, ammonium hydroxide etc..
In step 3), the pH value of the solution is 8-9.
In step 3), it is 3:100 that the additional amount of the platinum acid chloride solution, which is subject to and controls Pt:Sn atomic ratio,.
In step 4), the redox graphene solution, precursor solution mass percent be 1:50.
In step 4), the temperature of the hydrothermal synthesis reaction is 180-250 DEG C, reaction time 12-24h.The reaction temperature
Degree and time range can guarantee to obtain product SnO2, and graphene oxide is restored completely.
Preferably, the temperature of the hydrothermal synthesis reaction is 180 DEG C, time 16h.The reaction temperature and time will help
In the pattern of control reaction product.
In step 5), the parameter of the centrifuge separation are as follows: revolving speed 5000-8000r/min, time 10-20min.
Preferably, the parameter of the centrifuge separation are as follows: revolving speed 6500r/min, time 20min.
Preferably, it in step 5), repeats to rinse, be centrifuged, rinsing step each 5 times.
In step 6), the two steps drying condition are as follows: vacuum drying, first in 60 DEG C of baking 1-2h, then in 120 DEG C of baking 1-
3h。
In step 6), the annealing conditions are to keep the temperature 1-3h under 500-600 DEG C of nitrogen atmosphere.
Again, the invention discloses a kind of Pt/SnO of redox graphene package2Nano particle cluster gas sensing
The preparation method of device；Specifically, the preparation method comprises the following steps:
(1) by above-mentioned steps 5) in gum-like product be spin-coated in ceramic substrate using spin coating proceeding, obtain be coated with glue
The ceramic substrate of shape film；Then the drying of two step oven drying methods is carried out to it, is finally annealed.
(2) ceramics using the photoetching process of standard, metal deposition technique by Au electrode deposition in step (1) after annealing
On substrate, the Pt/SnO that the preparation of gas sensitive device unit and array is wrapped up to get redox graphene is formed2Nano particle group
Cluster gas sensor.
In step (1), the parameter of the spin coating proceeding are as follows: low speed 600-800r/min, high speed 3000-5000r/min；When
Between be respectively 30-40s, 40-60s.
Preferably, the parameter of spin coating proceeding are as follows: low speed 650r/min, high speed 4000r/min；Time is respectively 30s, 60s.
In step (1), the gel-like film with a thickness of 1.5-3.0um, the thickness of film is maintained in the thickness range
The generation of face crack can be effectively reduced, and increase substantially the sensitive property of device.
In step (1), the two steps drying condition are as follows: vacuum drying, first in 60 DEG C of baking 1-2h, then in 120 DEG C of baking 1-
3h。
In step (1), the annealing conditions are as follows: keep the temperature 1-3h under 500-600 DEG C of nitrogen atmosphere.
In step (2), the Au electrode with a thickness of 200-350nm.
Preferably, the Au electrode with a thickness of 300nm.
Finally, the invention discloses the Pt/SnO of above-mentioned redox graphene package2Nano particle cluster and its preparation
The application of method and the sensor of nano particle cluster preparation, the application include for methanol gas detection, environment inspection
It surveys, production safety detects, in field of taking precautions against natural calamities.
Compared with prior art, the present invention achieve it is following the utility model has the advantages that
(1) present invention prepares the Pt/SnO of redox graphene package using simple chemical synthesis mode2Nanometer
Grain cluster plays the metal-doped spills-over effects of Pt, reduces the boundary barrier potential of the composite material, produce highly sensitive methanol
Sensor.
(2) pass through hydroiodic acid solution in the present invention by graphene oxide partial reduction, then in conjunction with hydro-thermal and nitrogen atmosphere
Reducing degree is improved, redox graphene is obtained, improves the specific surface area of the composite construction, the speed of electric charge transfer, is improved
Highly sensitive sensitive at 110 DEG C of Optimization Work temperature, controllability height, before great industrialization is realized in sensitivity based on this structure
Scape.
(3) preparation method of the invention is controllable, chemical synthesis ratio is controllable, sets by reasonable raw material and special appearance
Meter obtains the Sensitive Apparatus of highly sensitive, low operating temperature, preparation process can by building hetero-junctions and metal spills-over effects
It repeats, there is biggish industrial application value.
(4) the also expansible formation gas sensor array of the technology of the present invention, technological operation are simple, controllable.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the element manufacturing flow chart of methanol sensor of the invention.
Fig. 2 is the Pt/SnO of redox graphene prepared by the present invention package2The structural schematic diagram of nano particle cluster.
Fig. 3 is the Pt/SnO of GO, pure stannic oxide and the redox graphene package prepared in the embodiment of the present invention 12
The X-ray diffractogram of nano particle cluster.
Fig. 4 is the Pt/SnO of redox graphene package in the embodiment of the present invention 12The SEM and EDS of nano particle cluster
Figure；Wherein, Fig. 4 (a) is SEM figure, and illustration is high-resolution SEM figure；Fig. 4 (b) is EDS figure.
Fig. 5 is the resistance variations response diagram of the methanol sensor prepared in the embodiment of the present invention 1.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
It should be understood that graphene oxide described in the present invention and embodiment passes through modified Hummers legal system
It is standby.
As described in background, that there are sensitivity is low, operating temperature is high, high production cost, preparation for existing sensor
The problems such as complex process, therefore, the present invention provides a kind of Pt/SnO of redox graphene package2Nano particle cluster gas
Dependent sensor and preparation method thereof, now in conjunction with the drawings and the specific embodiments, the present invention is described further.
Embodiment 1:
1, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster；The following steps are included:
1) SnCl of 100mL is taken4·5H2O dissolves in methanol solution, stirs 60min, obtains homogeneous transparent solution, then will
The dimethylformamide of 5mL is mixed with above-mentioned clear solution, obtains mixed liquor.
2) 5g graphene oxide powder is added in 120mL deionized water, the hydrogen for being 5mg/mL with concentration after ultrasonic disperse
Iodic acid solution carries out reduction treatment, obtains redox graphene solution.
3) it configures precursor solution: platinum acid chloride solution is added in the mixed liquor of step 1), control Pt:Sn atomic ratio
In 3:100；Then NaOH is added, solution pH value is adjusted to 8, obtains milky precursor solution.
4) the redox graphene solution in step 2) is mixed into (mass percent with the precursor solution in step 3)
After 1:50), it is added in the container that liner is polytetrafluoroethylene (PTFE), the hydrothermal synthesis 16h at 200 DEG C.
5) hydrothermal synthesis reaction in step 4) is finished and is put into solution and is centrifuged, revolving speed control in 6000r/min,
Time is 10min, and ethyl alcohol and deionized water are used after separation, repeats to rinse respectively, centrifugation, rinse 5 times, obtains gum-like product.
6) by the gum-like product in step 5) first in 60 DEG C of baking 2h, then in 120 DEG C of baking 2h, last 550 DEG C of nitrogen atmosphere
Enclose the Pt/SnO that lower annealing 2h wraps up to get redox graphene2Nano particle cluster.
2, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster gas sensor, packet
Include following steps:
(1) by above-mentioned steps 5) in gum-like product be spin-coated in ceramic substrate using spin coating proceeding, the ginseng of spin coating proceeding
Number are as follows: low speed 650r/min, high speed 4000r/min；Time is respectively 30s, 60s, obtains the gel-like film coated with 2mm thickness
Ceramic substrate；Then the ceramic substrate of gel-like film will be coated with first in 60 DEG C of baking 2h, then in 120 DEG C of baking 2h, last 550 DEG C
Nitrogen atmosphere under anneal 2h.
(2) ceramics using the photoetching process of standard, metal deposition technique by Au electrode deposition in step (1) after annealing
On substrate, formed gas sensitive device unit and array preparation, wherein Au electrode with a thickness of 300nm to get reduction-oxidation graphite
The Pt/SnO of alkene package2Nano particle cluster gas sensor.
The Pt/SnO of redox graphene package manufactured in the present embodiment2Nano particle cluster is class nucleocapsid composite junction
Structure；Wherein, Pt atom is evenly distributed on SnO2Surface, form kernel, redox graphene is coated on entirely as shell
The surface of kernel, structural schematic diagram are as shown in Figure 2.
The Pt/SnO that the redox graphene that gas sensor is used to prepare obtained in the present embodiment is wrapped up2Nanometer
Particle clusters carry out XRD, SEM, EDS test, as a result as shown in Figure 3,4 respectively.As can be seen from Figure 3 pass through simple hydro-thermal
Method has synthesized RGO/Pt/SnO2Composite material, there is no change stannic oxide rutile structure for the incorporation of GO and Pt element.Pt member
The incorporation of element is with Pt metal simple-substance and PtO2Form exist.Grain size size is computed in 10nm or so.Pass through Fig. 4 institute
Show, it can be seen that the presence of RGO enwrapped granule, particle size distribution is uniform, and presentation GO film is shell, Pt/SnO2Particle is core
Structure, which can effectively improve the air-sensitive performance of methanol, and reduce air-sensitive operating temperature.
Under conditions of operating temperature is 110 DEG C, methanol concentration 10ppm-500ppm, air-sensitive manufactured in the present embodiment is passed
Sensor is measured in real time device using air-sensitive test macro, as a result as shown in Figure 5.As can be seen from Figure 5: in 40ppm
It is respectively 6s and 21s to the air-sensitive response time of methanol and recovery time under concentration, high sensitivity is up to 60.Compared to similar biography
The sensor device performance fast response time, detection is accurate, and energy consumption, expanded application field, additionally by comparison can be effectively reduced
The gas of other classes of volatilizing responds discovery, and the structure design of this sensitive material has selective well to methanol.
Embodiment 2:
1, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster；The following steps are included:
1) SnCl of 100mL is taken2·2H2O dissolves in methanol solution, stirs 30min, obtains homogeneous transparent solution, then will
The dimethylformamide of 10mL is mixed with above-mentioned clear solution, obtains mixed liquor.
2) 5g graphene oxide powder is added in 120mL deionized water, the hydrogen for being 1mg/mL with concentration after ultrasonic disperse
Iodic acid solution carries out reduction treatment, obtains redox graphene solution.
3) it configures precursor solution: platinum acid chloride solution is added in the mixed liquor of step 1), control Pt:Sn atomic ratio
In 3:100；Then KOH is added, solution pH value is adjusted to 8.5, obtains milky precursor solution.
4) the redox graphene solution in step 2) is mixed into (mass percent with the precursor solution in step 3)
After 1:50), it is added in the container that liner is polytetrafluoroethylene (PTFE), the hydrothermal synthesis 16h at 180 DEG C.
5) hydrothermal synthesis reaction in step 4) is finished and is put into
It being centrifuged, revolving speed is controlled in 6500r/min, time 20min, ethyl alcohol and deionized water are used after separation,
It repeats to rinse respectively, centrifugation, rinse 5 times, obtain gum-like product.
6) by the gum-like product in step 5) first in 60 DEG C of baking 1h, then in 120 DEG C of baking 1h, last 500 DEG C of nitrogen atmosphere
Enclose the Pt/SnO that lower annealing 3h wraps up to get redox graphene2Nano particle cluster.
2, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster gas sensor, packet
Include following steps:
(1) by above-mentioned steps 5) in gum-like product be spin-coated in ceramic substrate using spin coating proceeding, the ginseng of spin coating proceeding
Number are as follows: low speed 600r/min, high speed 3000r/min；Time is respectively 40s, 40s, obtains the gel-like film coated with 3mm thickness
Ceramic substrate；Then the ceramic substrate of gel-like film will be coated with first in 60 DEG C of baking 1h, then in 120 DEG C of baking 1h, last 500 DEG C
Nitrogen atmosphere under anneal 3h.
(2) ceramics using the photoetching process of standard, metal deposition technique by Au electrode deposition in step (1) after annealing
On substrate, formed gas sensitive device unit and array preparation, wherein Au electrode with a thickness of 200nm to get reduction-oxidation graphite
The Pt/SnO of alkene package2Nano particle cluster gas sensor.
The Pt/SnO of redox graphene package manufactured in the present embodiment2Nano particle cluster is class nucleocapsid composite junction
Structure；Wherein, Pt atom is evenly distributed on SnO2Surface, form kernel, redox graphene is coated on entirely as shell
The surface of kernel.
Embodiment 3:
1, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster；The following steps are included:
1) SnCl of 120mL is taken4It dissolves in methanol solution, stirs 120min, homogeneous transparent solution is obtained, then by 4mL
Dimethylformamide mixed with above-mentioned clear solution, obtain mixed liquor.
2) 5g graphene oxide powder is added in 120mL deionized water, the hydrogen for being 3mg/mL with concentration after ultrasonic disperse
Iodic acid solution carries out reduction treatment, obtains redox graphene solution.
3) it configures precursor solution: platinum acid chloride solution is added in the mixed liquor of step 1), control Pt:Sn atomic ratio
In 3:100；Then ammonium hydroxide is added, solution pH value is adjusted to 9, obtains milky precursor solution.
4) the redox graphene solution in step 2) is mixed into (mass percent with the precursor solution in step 3)
After 1:50), it is added in the container that liner is polytetrafluoroethylene (PTFE), the hydrothermal synthesis 12h at 250 DEG C.
5) hydrothermal synthesis reaction in step 4) is finished and is put into solution and is centrifuged, revolving speed control in 5000r/min,
Time is 20min, and ethyl alcohol and deionized water are used after separation, repeats to rinse respectively, centrifugation, rinse 5 times, obtains gum-like product.
6) by the gum-like product in step 5) first in 60 DEG C of baking 1.5h, then in 120 DEG C of baking 1.5h, last 600 DEG C of nitrogen
Atmosphere encloses the Pt/SnO that lower annealing 1h wraps up to get redox graphene2Nano particle cluster.
2, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster gas sensor, packet
Include following steps:
(1) by above-mentioned steps 5) in gum-like product be spin-coated in ceramic substrate using spin coating proceeding, the ginseng of spin coating proceeding
Number are as follows: low speed 800r/min, high speed 5000r/min；Time is respectively 35s, 50s, and it is thin to obtain the glue coated with 1.5mm thickness
The ceramic substrate of film；Then the ceramic substrate for being coated with gel-like film is first in 60 DEG C of baking 1.5h, then in 120 DEG C of baking 1.5h, most
Anneal under 600 DEG C of nitrogen atmosphere 1h afterwards.
(2) ceramics using the photoetching process of standard, metal deposition technique by Au electrode deposition in step (1) after annealing
On substrate, formed gas sensitive device unit and array preparation, wherein Au electrode with a thickness of 350nm to get reduction-oxidation graphite
The Pt/SnO of alkene package2Nano particle cluster gas sensor.
The Pt/SnO of redox graphene package manufactured in the present embodiment2Nano particle cluster is class nucleocapsid composite junction
Structure；Wherein, Pt atom is evenly distributed on SnO2Surface, form kernel, redox graphene is coated on entirely as shell
The surface of kernel.
Embodiment 4:
1, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster；The following steps are included:
1) it takes the dimethyltin chloride of 150mL to dissolve in methanol solution, stirs 80min, obtain homogeneous transparent solution, so
The dimethylformamide of 10mL is mixed with above-mentioned clear solution afterwards, obtains mixed liquor.
2) 5g graphene oxide powder is added in 120mL deionized water, the hydrogen for being 4mg/mL with concentration after ultrasonic disperse
Iodic acid solution carries out reduction treatment, obtains redox graphene solution.
3) it configures precursor solution: platinum acid chloride solution is added in the mixed liquor of step 1), control Pt:Sn atomic ratio
In 3:100；Then ammonium hydroxide is added, solution pH value is adjusted to 9, obtains milky precursor solution.
4) the redox graphene solution in step 2) is mixed into (mass percent with the precursor solution in step 3)
After 1:50), it is added in the container that liner is polytetrafluoroethylene (PTFE), hydrothermal synthesis is for 24 hours at 250 DEG C.
5) hydrothermal synthesis reaction in step 4) is finished and is put into solution and is centrifuged, revolving speed control in 8000r/min,
Time is 10min, and ethyl alcohol and deionized water are used after separation, repeats to rinse respectively, centrifugation, rinse 5 times, obtains gum-like product.
6) by the gum-like product in step 5) first in 60 DEG C of baking 1.5h, then in 120 DEG C of baking 1.5h, last 580 DEG C of nitrogen
Atmosphere encloses the Pt/SnO that lower annealing 1.5h wraps up to get redox graphene2Nano particle cluster.
2, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster gas sensor, packet
Include following steps:
(1) by above-mentioned steps 5) in gum-like product be spin-coated in ceramic substrate using spin coating proceeding, the ginseng of spin coating proceeding
Number are as follows: low speed 700r/min, high speed 4500r/min；Time is respectively 40s, 55s, obtains the gel-like film coated with 2mm thickness
Ceramic substrate；Then the ceramic substrate for being coated with gel-like film is first in 60 DEG C of baking 1.5h, then in 120 DEG C of baking 1.5h, finally
Anneal 1.5h under 580 DEG C of nitrogen atmosphere.
(2) ceramics using the photoetching process of standard, metal deposition technique by Au electrode deposition in step (1) after annealing
On substrate, formed gas sensitive device unit and array preparation, wherein Au electrode with a thickness of 250nm to get reduction-oxidation graphite
The Pt/SnO of alkene package2Nano particle cluster gas sensor.
The Pt/SnO of redox graphene package manufactured in the present embodiment2Nano particle cluster cluster is that class nucleocapsid is compound
Structure；Wherein, Pt atom is evenly distributed on SnO2Surface, aggregation become particle clusters as kernel, redox graphene
The surface of entire kernel is coated on as shell.
Embodiment 5:
1, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster cluster；Including following
Step:
1) SnCl of 100mL is taken4·5H2O dissolves in methanol solution, stirs 100min, obtains homogeneous transparent solution, then
The dimethylformamide of 4mL is mixed with above-mentioned clear solution, obtains mixed liquor.
2) 5g graphene oxide powder is added in 120mL deionized water, the hydrogen for being 2mg/mL with concentration after ultrasonic disperse
Iodic acid solution carries out reduction treatment, obtains redox graphene solution.
3) it configures precursor solution: platinum acid chloride solution is added in the mixed liquor of step 1), control Pt:Sn atomic ratio
In 3:100；Then NaOH is added, solution pH value is adjusted to 8, obtains milky precursor solution.
4) the redox graphene solution in step 2) is mixed into (mass percent with the precursor solution in step 3)
After 1:50), it is added in the container that liner is polytetrafluoroethylene (PTFE), the hydrothermal synthesis 18h at 230 DEG C.
5) hydrothermal synthesis reaction in step 4) is finished and is put into solution and is centrifuged, revolving speed control in 7500r/min,
Time is 12min, and ethyl alcohol and deionized water are used after separation, repeats to rinse respectively, centrifugation, rinse 5 times, obtains gum-like product.
6) by the gum-like product in step 5) first in 60 DEG C of baking 1.5h, then in 120 DEG C of baking 1.5h, last 580 DEG C of nitrogen
Atmosphere encloses the Pt/SnO that lower annealing 1.5h wraps up to get redox graphene2Nano particle cluster.
2, a kind of Pt/SnO of redox graphene package2The preparation method of nano particle cluster gas sensor, packet
Include following steps:
(1) by above-mentioned steps 5) in gum-like product be spin-coated in ceramic substrate using spin coating proceeding, the ginseng of spin coating proceeding
Number are as follows: low speed 700r/min, high speed 4500r/min；Time is respectively 40s, 55s, obtains the gel-like film coated with 2mm thickness
Ceramic substrate；Then the ceramic substrate for being coated with gel-like film is first in 60 DEG C of baking 1.5h, then in 120 DEG C of baking 1.5h, finally
Anneal 1.5h under 580 DEG C of nitrogen atmosphere.
(2) ceramics using the photoetching process of standard, metal deposition technique by Au electrode deposition in step (1) after annealing
On substrate, formed gas sensitive device unit and array preparation, wherein Au electrode with a thickness of 250nm to get reduction-oxidation graphite
The Pt/SnO of alkene package2Nano particle cluster gas sensor.
The Pt/SnO of redox graphene package manufactured in the present embodiment2Nano particle cluster is class nucleocapsid composite junction
Structure；Wherein, Pt atom is evenly distributed on SnO2Surface, form kernel, redox graphene is coated on entirely as shell
The surface of kernel.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, for those skilled in the art
For member, various changes and changes are possible in this application.Within the spirit and principles of this application, it is made it is any modification,
Equivalent replacement, improvement etc., should be included within the scope of protection of this application.
Claims (18)
1. a kind of Pt/SnO of redox graphene package2Nano particle cluster, it is characterised in that: the nano particle cluster
For class core-shell structure, wherein pt atom is evenly distributed on the surface of stannic oxide, forms kernel, redox graphene
The surface of entire kernel is coated on as shell.
2. a kind of Pt/SnO of redox graphene package as described in claim 12The preparation method of nano particle cluster,
It is characterized by: the preparation method comprises the following steps:
1) it takes a certain amount of water-soluble stannide to dissolve in solvent, stirs, homogeneous transparent solution is obtained, then by a certain amount of two
Methylformamide is mixed with above-mentioned clear solution, obtains mixed liquor；
2) graphene oxide powder is added in deionized water, carries out reduction treatment with hydroiodic acid solution after ultrasonic disperse, obtains
Redox graphene solution；
3) it prepares precursor solution: a certain amount of platinum acid chloride solution being taken to be added in the mixed liquor of step 1), alkalinity is then added
Solution pH value is adjusted to alkalinity, obtains milky precursor solution by substance；
4) after mixing the redox graphene solution in step 2) with the precursor solution in step 3), it is poly- that liner, which is added,
Hydrothermal synthesis reaction is carried out in the container of tetrafluoroethene；
5) solution finished to hydrothermal synthesis reaction in step 4) is centrifuged, and ethyl alcohol and deionized water are used after separation, point
It Chong Fu not rinse, be centrifuged, rinsing step, obtain gum-like product；
6) gum-like product in step 5) is dried by two step oven drying methods, is then annealed to get air-sensitive biography is used to prepare
The Pt/SnO of the redox graphene package of sensor2Nano particle cluster.
3. the Pt/SnO of redox graphene package as claimed in claim 22The preparation method of nano particle cluster, it is special
Sign is: in step 1), the water solubility stannide includes: SnCl4·5H2O、SnCl2·2H2O、SnCl4, dimethyl dichloride
One of tin；The solvent is methanol solution；The mixing time is 30-120min；The solvent and dimethylformamide
Volume ratio be 10:1-30:1.
4. the Pt/SnO of redox graphene package as claimed in claim 32The preparation method of nano particle cluster, it is special
Sign is: the volume ratio of the solvent and dimethylformamide is 20:1.
5. the Pt/SnO of redox graphene package as claimed in claim 22The preparation method of nano particle cluster, it is special
Sign is: in step 2), the concentration of the redox graphene solution is 1-5mg/mL.
6. the Pt/SnO of redox graphene package as claimed in claim 22The preparation method of nano particle cluster, it is special
Sign is: in step 3), the alkaline matter includes: NaOH, KOH, any one in ammonium hydroxide；Presoma in the step 3)
The pH value of solution is 8-9；The additional amount of the platinum acid chloride solution controls Pt:Sn atomic ratio in 3:100.
7. such as the Pt/SnO of the described in any item redox graphene packages of claim 2-62The preparation side of nano particle cluster
Method, it is characterised in that: in step 4), the temperature of the hydrothermal synthesis reaction is 180-250 DEG C, reaction time 12-24h.
8. the Pt/SnO of redox graphene package as claimed in claim 72The preparation method of nano particle cluster, it is special
Sign is: the temperature of the hydrothermal synthesis reaction is 180 DEG C, time 16h；The redox graphene solution, presoma
The mass percent of solution is 1:50.
9. the Pt/SnO of redox graphene package as claimed in claim 22The preparation method of nano particle cluster, it is special
Sign is: in step 5), the parameter of the centrifuge separation are as follows: revolving speed 5000-8000r/min, time 10-20min.
10. the Pt/SnO of redox graphene package as claimed in claim 92The preparation method of nano particle cluster；It is special
Sign is: the parameter of the centrifuge separation are as follows: revolving speed 6500r/min, time 20min；It repeats to rinse, be centrifuged, rinsing step each 5
It is secondary.
11. the Pt/SnO of redox graphene package as claimed in claim 22The preparation method of nano particle cluster, it is special
Sign is: in step 6), the two steps drying condition are as follows: and vacuum drying, first in 60 DEG C of baking 1-2h, then in 120 DEG C of baking 1-3h；
The annealing conditions are to keep the temperature 1-3h under 500-600 DEG C of nitrogen atmosphere.
12. a kind of Pt/SnO for preparing redox graphene package2The method of nano particle cluster gas sensor, feature
It is: utilizes method as claimed in claim 2, specific steps are as follows:
(1) gum-like product in step 5) as claimed in claim 2 is spin-coated in ceramic substrate using spin coating proceeding, is applied
It is covered with the ceramic substrate of gel-like film；Then the drying of two step oven drying methods is carried out to it, is finally annealed；
(2) ceramic substrate using the photoetching process of standard, metal deposition technique by Au electrode deposition in step (1) after annealing
On, complete the Pt/SnO that the preparation of gas sensitive device unit and array is wrapped up to get redox graphene2Nano particle cluster gas
Dependent sensor.
13. preparing the Pt/SnO of redox graphene package as claimed in claim 122Nano particle cluster gas sensor
Method, it is characterised in that: in step (1), the parameter of the spin coating proceeding are as follows: low speed 600-800r/min, high speed 3000-
5000r/min；Time is respectively 30-40s, 40-60s；The gel-like film with a thickness of 1.5-3.0um；The two steps drying
Condition are as follows: vacuum drying, first in 60 DEG C of baking 1-2h, then in 120 DEG C of baking 1-3h；The annealing conditions are as follows: 500-600 DEG C of nitrogen
1-3h is kept the temperature under atmosphere；The Au electrode with a thickness of 200-350nm.
14. preparing the Pt/SnO of redox graphene package as claimed in claim 132Nano particle cluster gas sensor
Method, it is characterised in that: the parameter of spin coating proceeding are as follows: low speed 650r/min, high speed 4000r/min；Time be respectively 30s,
60s。
15. preparing the Pt/SnO of redox graphene package as claimed in claim 132Nano particle cluster gas sensor
Method, it is characterised in that: the Au electrode with a thickness of 300nm.
16. the Pt/SnO of redox graphene package as described in claim 12Nano particle cluster methanol gas detect,
Environment measuring, production safety detection, the application in field of taking precautions against natural calamities.
17. the Pt/SnO of redox graphene package as claimed in claim 22The preparation method of nano particle cluster is in first
Alcohol gas detection, environment measuring, production safety detection, the application in field of taking precautions against natural calamities.
18. preparing the Pt/SnO of redox graphene package as claimed in claim 122Nano particle cluster gas sensor
Method in methanol gas detection, environment measuring, production safety detection, the application in field of taking precautions against natural calamities.
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| CN110857928A (en) * | 2018-08-23 | 2020-03-03 | 吉福有限公司 | Semiconductor-type gas sensor, multi-sensor device, and method for identifying the same |
| CN110498405A (en) * | 2019-08-21 | 2019-11-26 | 南京倍格电子科技有限公司 | A kind of graphene/tin oxide composite air-sensitive material and preparation method thereof |
| CN110635120A (en) * | 2019-08-23 | 2019-12-31 | 上海海关工业品与原材料检测技术中心 | Tin dioxide/metal elementary substance/graphene ternary composite material and preparation method and application thereof |
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| CN112881488B (en) * | 2021-01-18 | 2022-06-24 | 天津理工大学 | Core-shell Au @ tin oxide/vertical graphene microelectrode and preparation method and application thereof |
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| US11688850B1 (en) | 2022-01-23 | 2023-06-27 | Guangdong University Of Technology | Preparation method of SnO2@Sn coated reduced graphene oxide composite material |
| CN114487020B (en) * | 2022-02-08 | 2023-12-22 | 扬州大学 | Gas-sensitive material for lung cancer breathing mark gas methanol and preparation method thereof |
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